CA2770914A1 - Filled polyurethane composites and methods of making same - Google Patents
Filled polyurethane composites and methods of making same Download PDFInfo
- Publication number
- CA2770914A1 CA2770914A1 CA2770914A CA2770914A CA2770914A1 CA 2770914 A1 CA2770914 A1 CA 2770914A1 CA 2770914 A CA2770914 A CA 2770914A CA 2770914 A CA2770914 A CA 2770914A CA 2770914 A1 CA2770914 A1 CA 2770914A1
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- CA
- Canada
- Prior art keywords
- hydroxyl number
- polyol
- composite material
- polyols
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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- 239000002131 composite material Substances 0.000 title claims abstract description 164
- 239000004814 polyurethane Substances 0.000 title claims abstract description 46
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 42
- 229920005862 polyol Polymers 0.000 claims abstract description 194
- 150000003077 polyols Chemical class 0.000 claims abstract description 194
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 126
- 239000012948 isocyanate Substances 0.000 claims abstract description 58
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 52
- 239000010881 fly ash Substances 0.000 claims abstract description 39
- 239000010883 coal ash Substances 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 230000007613 environmental effect Effects 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 25
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 24
- 239000004359 castor oil Substances 0.000 claims description 22
- 239000003549 soybean oil Substances 0.000 claims description 22
- 235000012424 soybean oil Nutrition 0.000 claims description 22
- 235000019438 castor oil Nutrition 0.000 claims description 21
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 21
- 229920005906 polyester polyol Polymers 0.000 claims description 21
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 17
- 229920000570 polyether Polymers 0.000 claims description 17
- 235000011187 glycerol Nutrition 0.000 claims description 12
- 229920000728 polyester Polymers 0.000 claims description 12
- 239000005056 polyisocyanate Substances 0.000 claims description 12
- 229920001228 polyisocyanate Polymers 0.000 claims description 12
- 241000196324 Embryophyta Species 0.000 claims description 11
- 239000004566 building material Substances 0.000 claims description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims description 9
- 239000003365 glass fiber Substances 0.000 claims description 5
- -1 fly ash) Chemical class 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000000945 filler Substances 0.000 description 22
- 239000000835 fiber Substances 0.000 description 16
- 239000004094 surface-active agent Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000006260 foam Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 238000005187 foaming Methods 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 235000019198 oils Nutrition 0.000 description 8
- 239000004604 Blowing Agent Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 5
- 239000004970 Chain extender Substances 0.000 description 5
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 239000004088 foaming agent Substances 0.000 description 5
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000004971 Cross linker Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
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- 239000012784 inorganic fiber Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 description 2
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 241000390166 Physaria Species 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229920013701 VORANOL™ Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000004599 antimicrobial Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000012973 diazabicyclooctane Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- AXFVIWBTKYFOCY-UHFFFAOYSA-N 1-n,1-n,3-n,3-n-tetramethylbutane-1,3-diamine Chemical compound CN(C)C(C)CCN(C)C AXFVIWBTKYFOCY-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 1
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000010754 BS 2869 Class F Substances 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 241001520808 Panicum virgatum Species 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
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- 244000082204 Phyllostachys viridis Species 0.000 description 1
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- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
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- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
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- 229910000275 saponite Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000010435 syenite Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical group 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/16—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6662—Compounds of group C08G18/42 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K11/00—Use of ingredients of unknown constitution, e.g. undefined reaction products
- C08K11/005—Waste materials, e.g. treated or untreated sewage sludge
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Composite materials and methods for their preparation are described herein. The composite materials include a polyurethane made from the reaction of an isocyanate and a mixture of polyols, and coal ash (e.g., fly ash). The mixture of polyols comprises at least two polyols including a high hydroxyl number polyol having a hydroxyl number greater than 250 and comprising from about 1% to about 25% by weight of the total polyol content used to form the polyurethane, and a low hydroxyl number polyol having a hydroxyl number of 250 or lower. The coal ash is present in amounts from about 40% to about 90% by weight of the composite material. Also described is a method of preparing a composite material, including mixing an isocyanate, a mixture of at least two polyols, coal ash (e.g., fly ash), and a catalyst.
Description
FILLED POLYURETHANE COMPOSITES
AND METHODS OF MAKING SAME
BACKGROUND
Polymeric composite materials that contain organic or inorganic filler materials have become desirable for a variety of uses because of their excellent mechanical properties and weathering stability. Foamed versions of these materials can be relatively low density yet the filler materials can provide a composite material that is extremely strong. The polymer provided in the composite material can help provide good toughness (i.e., resistance to brittle fracture) and resistance to degradation from weathering to the composite when it is exposed to the environment.
Thus, polymeric composite materials including organic or inorganic fillers can be used in a variety of applications.
SUMMARY
Composite materials and methods for their preparation are described. The composite materials include a polyurethane formed by the reaction of an isocyanate and a polyol, and coal ash. The coal ash can be, for example, fly ash. The isocyanates used in these composites are selected from the group consisting of diisocyanates, polyisocyanates and mixtures thereof. The polyols used in these composites include at least two polyols, the at least two polyols including a high hydroxyl number polyol selected from the group consisting of polyether polyols and polyester polyols, the high hydroxyl number polyol having a hydroxyl number greater than 250 and comprising from about 1% to about 25% by weight of the total polyol content used to form the polyurethane, and a low hydroxyl number polyol selected from the group consisting of polyether polyols and polyester polyols, the low hydroxyl number polyol having a hydroxyl number of 250 or lower. The fly ash is present in amounts from about 40% to about 90% by weight of the composite material.
Also described is a method of preparing a composite material, which includes mixing an isocyanate selected from the group consisting of diisocyanates, polyisocyanates, and mixtures thereof, at least two polyols wherein the at least two polyols include (i) a high hydroxyl number polyol selected from the group consisting of polyether polyols and polyester polyols and having a first hydroxyl number greater than 250, said high hydroxyl number polyol comprising from about 1% to about 25%
by weight of the total polyol content used to form the polyurethane, and (ii) a lower hydroxyl number polyol selected from the group consisting of polyether polyols and polyester polyols, said lower hydroxyl number polyol having a hydroxyl number of 250 or lower; coal ash; and a catalyst. The coal ash can be, for example, fly ash. The isocyanate and the at least two polyols react in the presence of the coal ash and catalyst to form the composite material. The amount of coal ash (e.g., fly ash) added in the mixing step is from about 40% to about 90% by weight of the composite material.
DETAILED DESCRIPTION
Composite materials and methods for their preparation are described herein.
The composite materials include a polyurethane formed by the reaction of an isocyanate, selected from the group consisting of diisocyanates, polyisocyanates, and mixtures thereof, and at least two polyols. The at least two polyols include a high hydroxyl number polyol and a low hydroxyl number polyol and can be selected from polyether polyols and polyester polyols. The high hydroxyl number polyol has a hydroxyl number greater than 250 and is from about 1% to about 25% by weight of the total polyol content used to form the polyurethane. The low hydroxyl number polyol has a hydroxyl number of 250 or lower. Coal ash (e.g., fly ash) is present in the composite materials in amounts from about 40% to about 90% by weight of the composite material.
The composite materials described herein as well as their polyurethane component can be formulated with a high total environmental content. As used herein, the term total environmental content refers to the sum of the total renewable content and the total recyclable content used to form a composite material or its polyurethane component and is expressed as a weight percent. As used herein, renewable content refers to matter that is provided by natural processes or sources.
Examples of renewable content include alcohol and oils from plants, such as castor oil and soybean oil. Isocyanates derived from natural oil, such as castor oil pre-polymers and soybean oil pre-polymers, are also examples of renewable content. As used herein, recyclable content includes content that is derived from materials that would otherwise have been discarded. Examples of recyclable content include a recyclable polyol (e.g., one derived from recyclable polyester), glycerin sourced from a biodiesel plant, and a coal ash. Renewable content and recyclable content are used in the composites described herein to produce composite materials and polyurethane components with a high total environmental content.
The total environmental content of the polyurethane component (based only on the polyols and isocyanates) of the composite materials described herein can be greater than 35%. Further, the total environmental content of the polyurethane components described herein can be greater than 40% or greater than 45%.
Examples of the total environmental content of the polyurethane components include environmental content greater than 36%, greater than 37%, greater than 38%, greater than 39%, greater than 41%, greater than 42%, greater than 43%, and greater than 44%. Additionally, the total environmental content of the polyurethane components can be about 36%, about 37%, about 38%, about 39%, about 40%, about 41%, about 42%, about 43%, about 44%, about 45%, about 46%, about 47%, about 48%, about 49%, or about 50%. As used herein, the term about is intended to capture the range of experimental error (e.g., I%) associated with making the specified measurement.
Unless otherwise noted, all percentages and parts are by weight.
The total environmental content of the composite materials described herein can be greater than 75%. Further, the total environmental content of the composite materials described herein can be greater than 80% or greater than 85%.
Examples of the total environmental content of the composite materials include total environmental content greater than 76%, greater than 77%, greater than 78%, greater than 79%, greater than 81%, greater than 82%, greater than 83%, and greater than 84%.
Additionally, the total environmental content of the composite materials can be about 75%, about 76%, about 77%, about 78%, about 79%, about 80%, about 81%, about 82%, about 83%, about 84%, about 85%, about 86%, about 87%, about 88%, about 89%, or about 90%.
Polyurethanes useful with the composite materials described herein include those formed by the reaction of one or more monomeric, oligomeric poly- or di-isocyanates, or mixtures of these (sometimes referred to as isocyanates) and at least two polyols, the at least two polyols including a high hydroxyl number polyol and a low hydroxyl number polyol (both selected from the group consisting of polyether polyols and polyester polyols). The high hydroxyl number polyol has a hydroxyl number greater than 250 and is present in amounts from about 1% to about 25%
by weight of the total polyol content used to form the polyurethane. The low hydroxyl number polyol has a hydroxyl number of 250 or lower and is present in amounts from about 75% to about 99% by weight of the total polyol content used to form the polyurethane.
The high hydroxyl number polyol and/or the low hydroxyl number polyol can be a plant-based polyol and thus increase the environmental content of the polyurethane component and thus the composite material. The plant-based polyols can include polyols containing ester groups that are derived from plant-based fats and oils and can contain structural elements of fatty acids and fatty alcohols.
Starting materials for the plant-based polyols of the polyurethane component include fats and/or oils of plant-based origin with preferably unsaturated fatty acid residues. For example, the plant-based polyols can be or can be derived from castor oil, coconut oil, corn oil, cottonseed oil, lesquerella oil, linseed oil, olive oil, palm oil, palm kernel oil, peanut oil, sunflower oil, tall oil, or mixtures thereof.
The high hydroxyl number polyol (whether a single polyol or mixture of high hydroxyl number polyols) can be present in an amount from about I% to about 25%, about 1 % to about 20%, about 1 % to about 15 %, about 1 % to about 10%, or about 1 %
to about 5%. Examples of the weight percent of the high hydroxyl number in the mixtures include about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 16%, about 17%, about 18%, about 19%, about 20%, about 21%, about 22%, about 23%, about 24%, and about 25%. The low hydroxyl number polyol (whether a single polyol or mixture of low hydroxyl number polyols) can be, for example, from about 75% to about 99%, about 80% to about 99%, about 85% to about 99%, about 90% to about 99%, or about 95% to about 99% by weight of the total polyol content. For further example, the percentages of the low hydroxyl number polyol by weight of the total polyol can be about 75%, about 76%, about 77%, about 78%, about 79%, about 80%, about 81%, about 82%, about 83%, about 84%, about 85%, about 86%, about 87%, about 88%, about 89%, about 90%, about 91%, about 92%, about 93%, about 94%, about 95%, about 96%, about 97%, about 98%, or about 99%. For example, the high hydroxyl number can be present in 15%
by weight of the total polyol and the low hydroxyl number can be present in 85% by weight of the total polyol.
As indicated above, the high hydroxyl number polyol useful in the composite materials described herein has a hydroxyl number greater than 250. Examples of the high hydroxyl number polyol include hydroxyl numbers greater than 255, greater than 260, greater than 265, greater than 270, greater than 275, greater than 280, greater than 285, greater than 290, greater than 295, greater than 300, greater than 325, greater than 350, greater than 375, greater than 400, greater than 450, greater than 500, greater than 550, greater than 600, greater than 650, greater than 700, greater than 750, greater than 800, greater than 850, greater than 900, greater than 950, greater than 1000, greater than 1100, greater than 1200, greater than 1300, greater than 1400, greater than 1500, greater than 1600, greater than 1700, greater than 1800, greater than 1900, and greater than 2000. The high hydroxyl number polyols can have an average functionality of about 2.0 to about 8.0, about 2.2 to about 6.0, about 2.3 to about 5.0, about 2.4 to about 4.0, or about 2.5 to about 3.5.
Exemplary high hydroxyl number polyols include, for example, glycerin and other polyols typically considered chain extenders or cross-linking agents such as ethylene glycol, 1,4-butanediol, trimethylolpropane, and sorbitol. The high hydroxyl number polyols can include highly reactive polyols such as highly reactive soybean oil based polyols. In some embodiments, the highly reactive polyols can include a large number of primary hydroxyl groups (e.g. 75% or more or 80% or more) as determined using fluorine NMR spectroscopy as described in ASTM D4273 [34].
Suitable highly reactive polyols can produce a Brookfield viscosity rise to a Brookfield viscosity of over 50,000 cP in less than 225 seconds, or less than seconds when used in a standard Brookfield Viscosity Test procedure. In the standard Brookfield Viscosity Test procedure, the polyol is provided in an amount of 100 parts by weight and mixed with DC-197 surfactant (1.0 parts by weight), DABCO R-8020 catalyst (2.0 parts by weight), fly ash (460.0 parts by weight) and water (0.5 parts by weight) in a 600 mL glass jar at 1000 RPM for 30 seconds using any lab-duty electric stirrer equipped with a Jiffy Mixer brand, Model LM, mixing blade. MONDUR MR
Light (a polymeric MDI, having a NCO weight of 31.5%, viscosity of 200 mPa=s @
25 C, equivalent weight of 133, and a functionality of 2.8) is then added at an isocyanate index of 110 and the components mixed for an additional 30 seconds.
The glass jar is then removed from the stirrer and placed on a Brookfield viscometer. The viscosity rise is measured using a for 20 minutes or until 50,000 cP is reached. The Brookfield Viscosity Test is described, for example, in Polyurethane Handbook:
Chemistry, Raw Materials, Processing Application, Properties, 2nd Edition, Ed:
Gunter Oertel; Hanser/Gardner Publications, Inc., Cincinnati, OH; Rigid Plastic Foams, T.H. Ferrigno (1963); and Reaction Polymers: Polyurethanes, Epoxies, Unsaturated Polyesters, Phenolics, Special Monomers and Additives: Chemistry, Technology, Applications, Wilson F. Gum et al. (1992), which are all herein incorporated by reference. In some embodiments, the highly reactive polyol can have a primary hydroxyl number, defined as the hydroxyl number multiplied by the percentage of primary hydroxyl groups based on the total number of hydroxyl groups, of greater than 250. Exemplary highly reactive polyols include Pel-Soy 744 and Pel-Soy P-750, soybean oil based polyols commercially available from Pelron Corporation; Agrol Diamond, a soybean oil based polyol commercially available from BioBased Technologies; Ecopol 122, Ecopol 131 and Ecopol 132, soybean oil polyols formed using polyethylene terephthalate and commercially available from Ecopur Industries; Honey Bee HB-530, a soybean oil-based polyol commercially available from MCPU Polymer Engineering; Stepanpol PD-110 LV and PS 2352, polyols based on soybean oil, diethylene glycol and phthallic anhydride and commercially available from Stepan Company; and derivatives thereof. In some embodiments, the highly reactive polyols can be formed by the reaction of a soybean oil and a polyester to produce a plant-based polyester polyol. An example of such a soybean oil-based polyester polyol is Ecopol 131, which is a highly reactive aromatic polyester polyol comprising 80% primary hydroxyl groups. Polyester polyols can be prepared using recyclable polyester to further increase the recyclable content of a composite material and Ecopol 131 is an example of such a polyester polyol. In some embodiments, the soybean oil and polyester based polyol can be prepared using recycled polyester.
Further examples of high hydroxyl number polyols include Voranol 225, 360, 480, RN 490, RA 640, RA 800, 230-660 and WR2000, polyether polyols commercially available from Dow Chemical Company (Midland, MI); Multranol 4011, 4012 and 4050 and Arcol LG-56 and LG-650, commercially available from Bayer; Renewpol, commercially available from Styrotech Industries (Brooklyn Park, MN); JeffAdd B
650, a 65% bio-based content (using ASTM D6866-06) additive based on soybean oil commercially available from Huntsman Polyurethanes (Auburn Hills, MI); Jeffol SG
360, a sucrose and glycerin-based polyol commercially available from Huntsman Polyurethanes; and derivatives thereof. In some embodiments, the high hydroxyl number polyol can include renewable and recyclable content. The high hydroxyl number polyol can also be composed of a blend of high hydroxyl number polyols (e.g.
a blend of glycerin and Ecopol 131).
The low hydroxyl number polyol has a hydroxyl number of 250 or lower.
Examples of the low hydroxyl number polyol include hydroxyl numbers lower than 245, lower than 240, lower than 235, lower than 230, lower than 225, lower than 220, lower than 215, lower than 210, lower than 205, lower than 200, lower than 195, lower than 190, lower than 185, lower than 180, lower than 175, lower than 150, lower than 125, or lower than 100. The low hydroxyl number polyols can have an average functionality of about 1.0 to about 4.0, about 1.5 to about 3.5, about 1.8 to about 3.4, or about 2.0 to about 3Ø
Exemplary low hydroxyl number polyols include castor oil and lesquerella oil.
Castor oil is a well-known, commercially available material, and is described, for example, in Encyclopedia of Chemical Technology, Volume 5, John Wiley & Sons (1979). Suitable castor oils include those sold by Vertellus Specialties, Inc., e.g., DB Oil, which has a hydroxyl number of about 166, and Eagle Specialty Products, e.g., T31 Oil, which has a hydroxyl number of about 160. Other exemplary low hydroxyl number polyols that provide additional environmental content include Ecopol 123 and Ecopol 124, which are commercially available from Ecopur Industries; Agrol 2.0, 3.6, 4.3, 5.6 and 7.0, vegetable oil based polyols commercially available from BioBased Technologies; Honey Bee HB-150 and HB-230, soybean oil-based polyols commercially available from MCPU Polymer Engineering; and Terol 1154, commercially available from Oxid (Houston, TX). Other low hydroxyl number polyols can also be used such as Multranol 3900, Multranol 3901, Arcol 34, Arcol 24-32, Arcol 31-28, Arcol E-351, Arcol LHT-42, and Arcol LHT -112, commercially available from Bayer; Voranol 220-028, 220-094, 220-1 ION, 222-056, 232-027, 232-034, and 232-035, commercially available from Dow; and derivatives thereof. The low hydroxyl number polyol can also be composed of a blend of polyols. For example, the low hydroxyl number polyol can be a blend of castor oil and another low hydroxyl number polyol.
In some embodiments, a polyol system useful with the composite materials described herein can include 1-25% of glycerin (hydroxyl number: 1829 mg KOH/g), Ecopol 131 (hydroxyl number: 360-380 mg KOH/g), or a mixture thereof; and 75-99% castor oil (hydroxyl number: about 166 mg KOH/g).
Isocyanates useful with the composite materials described herein include one or more monomeric or oligomeric poly- or di-isocyanates. The monomeric or oligomeric poly- or di-isocyanate include aromatic diisocyanates and polyisocyanates.
The isocyanates can also be blocked isocyanates or pre-polymer isocyanates (e.g., castor oil pre-polymer isocyanates and soy polyol pre-polymer isocyanates). An example of a useful diisocyanate is methylene diphenyl diisocyanate (MDI).
Useful MDIs include MDI monomers, MDI oligomers, and mixtures thereof.
Further examples of useful isocyanates include those having NCO (i.e., the reactive group of an isocyanate) contents ranging from about 25% to about 35%
by weight. Examples of useful isocyanates are found, for example, in Polyurethane Handbook: Chemistry, Raw Materials, Processing Application, Properties, 2d Edition, Ed: Gunter Oertel; Hanser/Gardner Publications, Inc., Cincinnati, OH, which is herein incorporated by reference. Suitable examples of aromatic polyisocyanates include 2,4- or 2,6-toluene diisocyanate, including mixtures thereof; p-phenylene diisocyanate; tetramethylene and hexamethylene diisocyanates; 4,4-dicyclohexylmethane diisocyanate; isophorone diisocyanate; 4,4-phenylmethane diisocyanate; polymethylene polyphenylisocyanate; and mixtures thereof. In addition, triisocyanates may be used, for example, 4,4,4-triphenylmethane triisocyanate;
1,2,4-benzene triisocyanate; polymethylene polyphenyl polyisocyanate; methylene polyphenyl polyisocyanate; and mixtures thereof. Suitable blocked isocyanates are formed by the treatment of the isocyanates described herein with a blocking agent (e.g., diethyl malonate, 3,5-dimethylpyrazole, methylethylketoxime, and caprolactam). Isocyanates are commercially available, for example, from Bayer Corporation (Pittsburgh, PA) under the trademarks MONDUR and DESMODUR.
Other examples of suitable isocyanates include Mondur MR Light (Bayer Corporation; Pittsburgh, PA), PAPI 27 (Dow Chemical Company; Midland, MI), Lupranate M20 (BASF Corporation; Florham Park, NJ), Lupranate M70L (BASF
Corporation; Florham Park, NJ), Rubinate M (Huntsman Polyurethanes; Geismar, LA), Econate 31 (Ecopur Industries), and derivatives thereof.
The average functionality of isocyanates or combinations of isocyanates useful with the composites described herein is between about 1.5 to about 5. Further, examples of useful isocyanates include isocyanates with an average functionality of about 2 to 4.5, about 2.2 to about 4.0, about 2.4 to about 3.7, about 2.6 to about 3.4, and about 2.8 to about 3.2.
In general, the ratio of isocyanate groups to the total isocyanate reactive groups, such as hydroxyl groups, water and amine groups, is in the range of about 0.5:1 to about 1.5:1, which when multiplied by 100 produces an isocyanate index between 50 and 150. Additionally, the isocyanate index can be from about 80 to about 120, from about 90 to about 120, from about 100 to about 115, or from about 105 to about 110. As used herein, an isocyanate may be selected to provide a reduced isocyanate index, which can be reduced without compromising the chemical or mechanical properties of the composite material.
As described above, the composite materials described herein include a polyurethane formed by the reaction of an isocyanate and at least two polyols in the presence of coal ash. The coal ash can be fly ash, bottom ash, or combinations thereof. In some examples, the coal ash used is fly ash. Fly ash is produced from the combustion of pulverized coal in electrical power generating plants. The fly ash useful with the composite materials described herein can be Class C fly ash, Class F
fly ash, or a mixture thereof. Fly ash produced by coal-fueled power plants are suitable for incorporation in composites described herein.
Coal ash is present in the composites described herein in amounts from about 40% to about 90% by weight. Further, coal ash can be present in amounts from about 60% to about 85%. Examples of the amount of coal ash present in the composites described herein include about 40%, about 41%, about 42%, about 43%, about 44%, about 45%, about 46%, about 47%, about 48%, about 49%, about 50%, about 51%, about 52%, about 53%, about 54%, about 55%, about 56%, about 57%, about 58%, about 59%, about 60%, about 61%, about 62%, about 63%, about 64%, about 65%, about 66%, about 67%, about 68%, about 69%, about 70%, about 71%, about 72%, about 73%, about 74%, about 75%, about 76%, about 77%, about 78%, about 79%, about 80%, about 81%, about 82%, about 83%, about 84%, about 85%, about 86%, about 87%, about 88%, about 89%, or about 90%.
One or more additional fillers can be used in the composite materials described herein. Examples of fillers useful with the composite materials include other types of ash such as those produced by firing fuels including industrial gases, petroleum coke, petroleum products, municipal solid waste, paper sludge, wood, sawdust, refuse derived fuels, switchgrass, or other biomass material. The one or more additional fillers can also include ground/recycled glass (e.g., window or bottle glass); milled glass; glass spheres; glass flakes; activated carbon; calcium carbonate;
aluminum trihydrate (ATH); silica; sand; ground sand; silica fume; slate dust;
crusher fines; red mud; amorphous carbon (e.g., carbon black); clays (e.g., kaolin);
mica; talc;
wollastonite; alumina; feldspar; bentonite; quartz; garnet; saponite;
beidellite; granite;
calcium oxide; calcium hydroxide; antimony trioxide; barium sulfate; magnesium oxide; titanium dioxide; zinc carbonate; zinc oxide; nepheline syenite;
perlite;
diatomite; pyrophillite; flue gas desulfurization (FGD) material; soda ash;
trona;
inorganic fibers; soy meal; pulverized foam; and mixtures thereof.
In some embodiments, inorganic fibers or organic fibers can be included in the polymer composite, e.g., to provide increased strength, stiffness or toughness. Fibers suitable for use with the composite materials described herein can be provided in the form of individual fibers, fabrics, rovings, or tows. These can be added prior to polymerization and can be chopped before or during the mixing process to provide desired fiber lengths. Alternately, the fibers can be added after polymerization, for example, after the composite material exits the mixing apparatus. The fibers can be up to about 2 in. in length. The fibers can be provided in a random orientation or can be axially oriented. The fibers can be coated with a sizing to modify performance to make the fibers reactive. Exemplary fibers include glass, polyvinyl alcohol (PVA), carbon, basalt, wollastonite, and natural (e.g., bamboo or coconut) fibers.
AND METHODS OF MAKING SAME
BACKGROUND
Polymeric composite materials that contain organic or inorganic filler materials have become desirable for a variety of uses because of their excellent mechanical properties and weathering stability. Foamed versions of these materials can be relatively low density yet the filler materials can provide a composite material that is extremely strong. The polymer provided in the composite material can help provide good toughness (i.e., resistance to brittle fracture) and resistance to degradation from weathering to the composite when it is exposed to the environment.
Thus, polymeric composite materials including organic or inorganic fillers can be used in a variety of applications.
SUMMARY
Composite materials and methods for their preparation are described. The composite materials include a polyurethane formed by the reaction of an isocyanate and a polyol, and coal ash. The coal ash can be, for example, fly ash. The isocyanates used in these composites are selected from the group consisting of diisocyanates, polyisocyanates and mixtures thereof. The polyols used in these composites include at least two polyols, the at least two polyols including a high hydroxyl number polyol selected from the group consisting of polyether polyols and polyester polyols, the high hydroxyl number polyol having a hydroxyl number greater than 250 and comprising from about 1% to about 25% by weight of the total polyol content used to form the polyurethane, and a low hydroxyl number polyol selected from the group consisting of polyether polyols and polyester polyols, the low hydroxyl number polyol having a hydroxyl number of 250 or lower. The fly ash is present in amounts from about 40% to about 90% by weight of the composite material.
Also described is a method of preparing a composite material, which includes mixing an isocyanate selected from the group consisting of diisocyanates, polyisocyanates, and mixtures thereof, at least two polyols wherein the at least two polyols include (i) a high hydroxyl number polyol selected from the group consisting of polyether polyols and polyester polyols and having a first hydroxyl number greater than 250, said high hydroxyl number polyol comprising from about 1% to about 25%
by weight of the total polyol content used to form the polyurethane, and (ii) a lower hydroxyl number polyol selected from the group consisting of polyether polyols and polyester polyols, said lower hydroxyl number polyol having a hydroxyl number of 250 or lower; coal ash; and a catalyst. The coal ash can be, for example, fly ash. The isocyanate and the at least two polyols react in the presence of the coal ash and catalyst to form the composite material. The amount of coal ash (e.g., fly ash) added in the mixing step is from about 40% to about 90% by weight of the composite material.
DETAILED DESCRIPTION
Composite materials and methods for their preparation are described herein.
The composite materials include a polyurethane formed by the reaction of an isocyanate, selected from the group consisting of diisocyanates, polyisocyanates, and mixtures thereof, and at least two polyols. The at least two polyols include a high hydroxyl number polyol and a low hydroxyl number polyol and can be selected from polyether polyols and polyester polyols. The high hydroxyl number polyol has a hydroxyl number greater than 250 and is from about 1% to about 25% by weight of the total polyol content used to form the polyurethane. The low hydroxyl number polyol has a hydroxyl number of 250 or lower. Coal ash (e.g., fly ash) is present in the composite materials in amounts from about 40% to about 90% by weight of the composite material.
The composite materials described herein as well as their polyurethane component can be formulated with a high total environmental content. As used herein, the term total environmental content refers to the sum of the total renewable content and the total recyclable content used to form a composite material or its polyurethane component and is expressed as a weight percent. As used herein, renewable content refers to matter that is provided by natural processes or sources.
Examples of renewable content include alcohol and oils from plants, such as castor oil and soybean oil. Isocyanates derived from natural oil, such as castor oil pre-polymers and soybean oil pre-polymers, are also examples of renewable content. As used herein, recyclable content includes content that is derived from materials that would otherwise have been discarded. Examples of recyclable content include a recyclable polyol (e.g., one derived from recyclable polyester), glycerin sourced from a biodiesel plant, and a coal ash. Renewable content and recyclable content are used in the composites described herein to produce composite materials and polyurethane components with a high total environmental content.
The total environmental content of the polyurethane component (based only on the polyols and isocyanates) of the composite materials described herein can be greater than 35%. Further, the total environmental content of the polyurethane components described herein can be greater than 40% or greater than 45%.
Examples of the total environmental content of the polyurethane components include environmental content greater than 36%, greater than 37%, greater than 38%, greater than 39%, greater than 41%, greater than 42%, greater than 43%, and greater than 44%. Additionally, the total environmental content of the polyurethane components can be about 36%, about 37%, about 38%, about 39%, about 40%, about 41%, about 42%, about 43%, about 44%, about 45%, about 46%, about 47%, about 48%, about 49%, or about 50%. As used herein, the term about is intended to capture the range of experimental error (e.g., I%) associated with making the specified measurement.
Unless otherwise noted, all percentages and parts are by weight.
The total environmental content of the composite materials described herein can be greater than 75%. Further, the total environmental content of the composite materials described herein can be greater than 80% or greater than 85%.
Examples of the total environmental content of the composite materials include total environmental content greater than 76%, greater than 77%, greater than 78%, greater than 79%, greater than 81%, greater than 82%, greater than 83%, and greater than 84%.
Additionally, the total environmental content of the composite materials can be about 75%, about 76%, about 77%, about 78%, about 79%, about 80%, about 81%, about 82%, about 83%, about 84%, about 85%, about 86%, about 87%, about 88%, about 89%, or about 90%.
Polyurethanes useful with the composite materials described herein include those formed by the reaction of one or more monomeric, oligomeric poly- or di-isocyanates, or mixtures of these (sometimes referred to as isocyanates) and at least two polyols, the at least two polyols including a high hydroxyl number polyol and a low hydroxyl number polyol (both selected from the group consisting of polyether polyols and polyester polyols). The high hydroxyl number polyol has a hydroxyl number greater than 250 and is present in amounts from about 1% to about 25%
by weight of the total polyol content used to form the polyurethane. The low hydroxyl number polyol has a hydroxyl number of 250 or lower and is present in amounts from about 75% to about 99% by weight of the total polyol content used to form the polyurethane.
The high hydroxyl number polyol and/or the low hydroxyl number polyol can be a plant-based polyol and thus increase the environmental content of the polyurethane component and thus the composite material. The plant-based polyols can include polyols containing ester groups that are derived from plant-based fats and oils and can contain structural elements of fatty acids and fatty alcohols.
Starting materials for the plant-based polyols of the polyurethane component include fats and/or oils of plant-based origin with preferably unsaturated fatty acid residues. For example, the plant-based polyols can be or can be derived from castor oil, coconut oil, corn oil, cottonseed oil, lesquerella oil, linseed oil, olive oil, palm oil, palm kernel oil, peanut oil, sunflower oil, tall oil, or mixtures thereof.
The high hydroxyl number polyol (whether a single polyol or mixture of high hydroxyl number polyols) can be present in an amount from about I% to about 25%, about 1 % to about 20%, about 1 % to about 15 %, about 1 % to about 10%, or about 1 %
to about 5%. Examples of the weight percent of the high hydroxyl number in the mixtures include about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 16%, about 17%, about 18%, about 19%, about 20%, about 21%, about 22%, about 23%, about 24%, and about 25%. The low hydroxyl number polyol (whether a single polyol or mixture of low hydroxyl number polyols) can be, for example, from about 75% to about 99%, about 80% to about 99%, about 85% to about 99%, about 90% to about 99%, or about 95% to about 99% by weight of the total polyol content. For further example, the percentages of the low hydroxyl number polyol by weight of the total polyol can be about 75%, about 76%, about 77%, about 78%, about 79%, about 80%, about 81%, about 82%, about 83%, about 84%, about 85%, about 86%, about 87%, about 88%, about 89%, about 90%, about 91%, about 92%, about 93%, about 94%, about 95%, about 96%, about 97%, about 98%, or about 99%. For example, the high hydroxyl number can be present in 15%
by weight of the total polyol and the low hydroxyl number can be present in 85% by weight of the total polyol.
As indicated above, the high hydroxyl number polyol useful in the composite materials described herein has a hydroxyl number greater than 250. Examples of the high hydroxyl number polyol include hydroxyl numbers greater than 255, greater than 260, greater than 265, greater than 270, greater than 275, greater than 280, greater than 285, greater than 290, greater than 295, greater than 300, greater than 325, greater than 350, greater than 375, greater than 400, greater than 450, greater than 500, greater than 550, greater than 600, greater than 650, greater than 700, greater than 750, greater than 800, greater than 850, greater than 900, greater than 950, greater than 1000, greater than 1100, greater than 1200, greater than 1300, greater than 1400, greater than 1500, greater than 1600, greater than 1700, greater than 1800, greater than 1900, and greater than 2000. The high hydroxyl number polyols can have an average functionality of about 2.0 to about 8.0, about 2.2 to about 6.0, about 2.3 to about 5.0, about 2.4 to about 4.0, or about 2.5 to about 3.5.
Exemplary high hydroxyl number polyols include, for example, glycerin and other polyols typically considered chain extenders or cross-linking agents such as ethylene glycol, 1,4-butanediol, trimethylolpropane, and sorbitol. The high hydroxyl number polyols can include highly reactive polyols such as highly reactive soybean oil based polyols. In some embodiments, the highly reactive polyols can include a large number of primary hydroxyl groups (e.g. 75% or more or 80% or more) as determined using fluorine NMR spectroscopy as described in ASTM D4273 [34].
Suitable highly reactive polyols can produce a Brookfield viscosity rise to a Brookfield viscosity of over 50,000 cP in less than 225 seconds, or less than seconds when used in a standard Brookfield Viscosity Test procedure. In the standard Brookfield Viscosity Test procedure, the polyol is provided in an amount of 100 parts by weight and mixed with DC-197 surfactant (1.0 parts by weight), DABCO R-8020 catalyst (2.0 parts by weight), fly ash (460.0 parts by weight) and water (0.5 parts by weight) in a 600 mL glass jar at 1000 RPM for 30 seconds using any lab-duty electric stirrer equipped with a Jiffy Mixer brand, Model LM, mixing blade. MONDUR MR
Light (a polymeric MDI, having a NCO weight of 31.5%, viscosity of 200 mPa=s @
25 C, equivalent weight of 133, and a functionality of 2.8) is then added at an isocyanate index of 110 and the components mixed for an additional 30 seconds.
The glass jar is then removed from the stirrer and placed on a Brookfield viscometer. The viscosity rise is measured using a for 20 minutes or until 50,000 cP is reached. The Brookfield Viscosity Test is described, for example, in Polyurethane Handbook:
Chemistry, Raw Materials, Processing Application, Properties, 2nd Edition, Ed:
Gunter Oertel; Hanser/Gardner Publications, Inc., Cincinnati, OH; Rigid Plastic Foams, T.H. Ferrigno (1963); and Reaction Polymers: Polyurethanes, Epoxies, Unsaturated Polyesters, Phenolics, Special Monomers and Additives: Chemistry, Technology, Applications, Wilson F. Gum et al. (1992), which are all herein incorporated by reference. In some embodiments, the highly reactive polyol can have a primary hydroxyl number, defined as the hydroxyl number multiplied by the percentage of primary hydroxyl groups based on the total number of hydroxyl groups, of greater than 250. Exemplary highly reactive polyols include Pel-Soy 744 and Pel-Soy P-750, soybean oil based polyols commercially available from Pelron Corporation; Agrol Diamond, a soybean oil based polyol commercially available from BioBased Technologies; Ecopol 122, Ecopol 131 and Ecopol 132, soybean oil polyols formed using polyethylene terephthalate and commercially available from Ecopur Industries; Honey Bee HB-530, a soybean oil-based polyol commercially available from MCPU Polymer Engineering; Stepanpol PD-110 LV and PS 2352, polyols based on soybean oil, diethylene glycol and phthallic anhydride and commercially available from Stepan Company; and derivatives thereof. In some embodiments, the highly reactive polyols can be formed by the reaction of a soybean oil and a polyester to produce a plant-based polyester polyol. An example of such a soybean oil-based polyester polyol is Ecopol 131, which is a highly reactive aromatic polyester polyol comprising 80% primary hydroxyl groups. Polyester polyols can be prepared using recyclable polyester to further increase the recyclable content of a composite material and Ecopol 131 is an example of such a polyester polyol. In some embodiments, the soybean oil and polyester based polyol can be prepared using recycled polyester.
Further examples of high hydroxyl number polyols include Voranol 225, 360, 480, RN 490, RA 640, RA 800, 230-660 and WR2000, polyether polyols commercially available from Dow Chemical Company (Midland, MI); Multranol 4011, 4012 and 4050 and Arcol LG-56 and LG-650, commercially available from Bayer; Renewpol, commercially available from Styrotech Industries (Brooklyn Park, MN); JeffAdd B
650, a 65% bio-based content (using ASTM D6866-06) additive based on soybean oil commercially available from Huntsman Polyurethanes (Auburn Hills, MI); Jeffol SG
360, a sucrose and glycerin-based polyol commercially available from Huntsman Polyurethanes; and derivatives thereof. In some embodiments, the high hydroxyl number polyol can include renewable and recyclable content. The high hydroxyl number polyol can also be composed of a blend of high hydroxyl number polyols (e.g.
a blend of glycerin and Ecopol 131).
The low hydroxyl number polyol has a hydroxyl number of 250 or lower.
Examples of the low hydroxyl number polyol include hydroxyl numbers lower than 245, lower than 240, lower than 235, lower than 230, lower than 225, lower than 220, lower than 215, lower than 210, lower than 205, lower than 200, lower than 195, lower than 190, lower than 185, lower than 180, lower than 175, lower than 150, lower than 125, or lower than 100. The low hydroxyl number polyols can have an average functionality of about 1.0 to about 4.0, about 1.5 to about 3.5, about 1.8 to about 3.4, or about 2.0 to about 3Ø
Exemplary low hydroxyl number polyols include castor oil and lesquerella oil.
Castor oil is a well-known, commercially available material, and is described, for example, in Encyclopedia of Chemical Technology, Volume 5, John Wiley & Sons (1979). Suitable castor oils include those sold by Vertellus Specialties, Inc., e.g., DB Oil, which has a hydroxyl number of about 166, and Eagle Specialty Products, e.g., T31 Oil, which has a hydroxyl number of about 160. Other exemplary low hydroxyl number polyols that provide additional environmental content include Ecopol 123 and Ecopol 124, which are commercially available from Ecopur Industries; Agrol 2.0, 3.6, 4.3, 5.6 and 7.0, vegetable oil based polyols commercially available from BioBased Technologies; Honey Bee HB-150 and HB-230, soybean oil-based polyols commercially available from MCPU Polymer Engineering; and Terol 1154, commercially available from Oxid (Houston, TX). Other low hydroxyl number polyols can also be used such as Multranol 3900, Multranol 3901, Arcol 34, Arcol 24-32, Arcol 31-28, Arcol E-351, Arcol LHT-42, and Arcol LHT -112, commercially available from Bayer; Voranol 220-028, 220-094, 220-1 ION, 222-056, 232-027, 232-034, and 232-035, commercially available from Dow; and derivatives thereof. The low hydroxyl number polyol can also be composed of a blend of polyols. For example, the low hydroxyl number polyol can be a blend of castor oil and another low hydroxyl number polyol.
In some embodiments, a polyol system useful with the composite materials described herein can include 1-25% of glycerin (hydroxyl number: 1829 mg KOH/g), Ecopol 131 (hydroxyl number: 360-380 mg KOH/g), or a mixture thereof; and 75-99% castor oil (hydroxyl number: about 166 mg KOH/g).
Isocyanates useful with the composite materials described herein include one or more monomeric or oligomeric poly- or di-isocyanates. The monomeric or oligomeric poly- or di-isocyanate include aromatic diisocyanates and polyisocyanates.
The isocyanates can also be blocked isocyanates or pre-polymer isocyanates (e.g., castor oil pre-polymer isocyanates and soy polyol pre-polymer isocyanates). An example of a useful diisocyanate is methylene diphenyl diisocyanate (MDI).
Useful MDIs include MDI monomers, MDI oligomers, and mixtures thereof.
Further examples of useful isocyanates include those having NCO (i.e., the reactive group of an isocyanate) contents ranging from about 25% to about 35%
by weight. Examples of useful isocyanates are found, for example, in Polyurethane Handbook: Chemistry, Raw Materials, Processing Application, Properties, 2d Edition, Ed: Gunter Oertel; Hanser/Gardner Publications, Inc., Cincinnati, OH, which is herein incorporated by reference. Suitable examples of aromatic polyisocyanates include 2,4- or 2,6-toluene diisocyanate, including mixtures thereof; p-phenylene diisocyanate; tetramethylene and hexamethylene diisocyanates; 4,4-dicyclohexylmethane diisocyanate; isophorone diisocyanate; 4,4-phenylmethane diisocyanate; polymethylene polyphenylisocyanate; and mixtures thereof. In addition, triisocyanates may be used, for example, 4,4,4-triphenylmethane triisocyanate;
1,2,4-benzene triisocyanate; polymethylene polyphenyl polyisocyanate; methylene polyphenyl polyisocyanate; and mixtures thereof. Suitable blocked isocyanates are formed by the treatment of the isocyanates described herein with a blocking agent (e.g., diethyl malonate, 3,5-dimethylpyrazole, methylethylketoxime, and caprolactam). Isocyanates are commercially available, for example, from Bayer Corporation (Pittsburgh, PA) under the trademarks MONDUR and DESMODUR.
Other examples of suitable isocyanates include Mondur MR Light (Bayer Corporation; Pittsburgh, PA), PAPI 27 (Dow Chemical Company; Midland, MI), Lupranate M20 (BASF Corporation; Florham Park, NJ), Lupranate M70L (BASF
Corporation; Florham Park, NJ), Rubinate M (Huntsman Polyurethanes; Geismar, LA), Econate 31 (Ecopur Industries), and derivatives thereof.
The average functionality of isocyanates or combinations of isocyanates useful with the composites described herein is between about 1.5 to about 5. Further, examples of useful isocyanates include isocyanates with an average functionality of about 2 to 4.5, about 2.2 to about 4.0, about 2.4 to about 3.7, about 2.6 to about 3.4, and about 2.8 to about 3.2.
In general, the ratio of isocyanate groups to the total isocyanate reactive groups, such as hydroxyl groups, water and amine groups, is in the range of about 0.5:1 to about 1.5:1, which when multiplied by 100 produces an isocyanate index between 50 and 150. Additionally, the isocyanate index can be from about 80 to about 120, from about 90 to about 120, from about 100 to about 115, or from about 105 to about 110. As used herein, an isocyanate may be selected to provide a reduced isocyanate index, which can be reduced without compromising the chemical or mechanical properties of the composite material.
As described above, the composite materials described herein include a polyurethane formed by the reaction of an isocyanate and at least two polyols in the presence of coal ash. The coal ash can be fly ash, bottom ash, or combinations thereof. In some examples, the coal ash used is fly ash. Fly ash is produced from the combustion of pulverized coal in electrical power generating plants. The fly ash useful with the composite materials described herein can be Class C fly ash, Class F
fly ash, or a mixture thereof. Fly ash produced by coal-fueled power plants are suitable for incorporation in composites described herein.
Coal ash is present in the composites described herein in amounts from about 40% to about 90% by weight. Further, coal ash can be present in amounts from about 60% to about 85%. Examples of the amount of coal ash present in the composites described herein include about 40%, about 41%, about 42%, about 43%, about 44%, about 45%, about 46%, about 47%, about 48%, about 49%, about 50%, about 51%, about 52%, about 53%, about 54%, about 55%, about 56%, about 57%, about 58%, about 59%, about 60%, about 61%, about 62%, about 63%, about 64%, about 65%, about 66%, about 67%, about 68%, about 69%, about 70%, about 71%, about 72%, about 73%, about 74%, about 75%, about 76%, about 77%, about 78%, about 79%, about 80%, about 81%, about 82%, about 83%, about 84%, about 85%, about 86%, about 87%, about 88%, about 89%, or about 90%.
One or more additional fillers can be used in the composite materials described herein. Examples of fillers useful with the composite materials include other types of ash such as those produced by firing fuels including industrial gases, petroleum coke, petroleum products, municipal solid waste, paper sludge, wood, sawdust, refuse derived fuels, switchgrass, or other biomass material. The one or more additional fillers can also include ground/recycled glass (e.g., window or bottle glass); milled glass; glass spheres; glass flakes; activated carbon; calcium carbonate;
aluminum trihydrate (ATH); silica; sand; ground sand; silica fume; slate dust;
crusher fines; red mud; amorphous carbon (e.g., carbon black); clays (e.g., kaolin);
mica; talc;
wollastonite; alumina; feldspar; bentonite; quartz; garnet; saponite;
beidellite; granite;
calcium oxide; calcium hydroxide; antimony trioxide; barium sulfate; magnesium oxide; titanium dioxide; zinc carbonate; zinc oxide; nepheline syenite;
perlite;
diatomite; pyrophillite; flue gas desulfurization (FGD) material; soda ash;
trona;
inorganic fibers; soy meal; pulverized foam; and mixtures thereof.
In some embodiments, inorganic fibers or organic fibers can be included in the polymer composite, e.g., to provide increased strength, stiffness or toughness. Fibers suitable for use with the composite materials described herein can be provided in the form of individual fibers, fabrics, rovings, or tows. These can be added prior to polymerization and can be chopped before or during the mixing process to provide desired fiber lengths. Alternately, the fibers can be added after polymerization, for example, after the composite material exits the mixing apparatus. The fibers can be up to about 2 in. in length. The fibers can be provided in a random orientation or can be axially oriented. The fibers can be coated with a sizing to modify performance to make the fibers reactive. Exemplary fibers include glass, polyvinyl alcohol (PVA), carbon, basalt, wollastonite, and natural (e.g., bamboo or coconut) fibers.
The inclusion of fillers in the composite materials as described herein can modify and/or improve the chemical and mechanical properties of the composite materials. For example, the optimization of various properties of the composite materials allows their use in building materials and other structural applications. High filler loading levels can be used in composite materials without a substantial reduction of (and potentially an improvement in) the intrinsic structural, physical, and mechanical properties of a composite.
The use of filled composites as building materials has advantages over composite materials made using lower filler levels or no filler. For example, the use of higher filler loading levels in building materials may allow the building materials to be produced at a substantially decreased cost. The use of large filler loadings also provides environmental advantages. For example, the incorporation of recyclable or renewable material, e.g., fly ash, as filler, provides a composite material with a higher percentage of environmentally friendly materials, i.e., a higher total environmental content. The use of the environmentally friendly materials in these composites decreases the need of landfills and other waste facilities to store such material.
Another environmental benefit of using recyclable or renewable materials as filler in these composites includes reducing the production of virgin fillers that may involve energy-intensive methods for their creation and may produce waste or by-product materials.
One or more catalysts are added to facilitate curing and can be used to control the curing time of the polymer matrix. Examples of useful catalysts include amine-containing catalysts (such as DABCO and tetramethylbutanediamine) and tin-, mercury-, and bismuth-containing catalysts. In some embodiments, 0.01 wt% to 2 wt% catalyst or catalyst system (e.g., 0.025 wt% to 1 wt%, 0.05 wt% to 0.5 wt %, or 0.1 wt% to about 0.25 wt%) can be used.
Additional components useful with the composite materials described herein include foaming agents, blowing agents, surfactants, chain-extenders, crosslinkers, coupling agents, UV stabilizers, fire retardants, antimicrobials, anti-oxidants, and pigments. Though the use of such components is well known to those of skill in the art, some of these additional additives are further described herein.
The use of filled composites as building materials has advantages over composite materials made using lower filler levels or no filler. For example, the use of higher filler loading levels in building materials may allow the building materials to be produced at a substantially decreased cost. The use of large filler loadings also provides environmental advantages. For example, the incorporation of recyclable or renewable material, e.g., fly ash, as filler, provides a composite material with a higher percentage of environmentally friendly materials, i.e., a higher total environmental content. The use of the environmentally friendly materials in these composites decreases the need of landfills and other waste facilities to store such material.
Another environmental benefit of using recyclable or renewable materials as filler in these composites includes reducing the production of virgin fillers that may involve energy-intensive methods for their creation and may produce waste or by-product materials.
One or more catalysts are added to facilitate curing and can be used to control the curing time of the polymer matrix. Examples of useful catalysts include amine-containing catalysts (such as DABCO and tetramethylbutanediamine) and tin-, mercury-, and bismuth-containing catalysts. In some embodiments, 0.01 wt% to 2 wt% catalyst or catalyst system (e.g., 0.025 wt% to 1 wt%, 0.05 wt% to 0.5 wt %, or 0.1 wt% to about 0.25 wt%) can be used.
Additional components useful with the composite materials described herein include foaming agents, blowing agents, surfactants, chain-extenders, crosslinkers, coupling agents, UV stabilizers, fire retardants, antimicrobials, anti-oxidants, and pigments. Though the use of such components is well known to those of skill in the art, some of these additional additives are further described herein.
Foaming agents and blowing agents may be added to the composite materials described herein to produce a foamed version of the composite materials.
Examples of blowing agents include organic blowing agents, such as halogenated hydrocarbons, acetone, hexanes, and other materials that have a boiling point below the reaction temperature. Chemical foaming agents include azodicarbonamides (e.g., Celogen manufactured by Lion Copolymer Geismar); and other materials that react at the reaction temperature to form gases such as carbon dioxide. Water is an exemplary foaming agent that reacts with isocyanate to yield carbon dioxide. The presence of water as an added component or in the filler also can result in the formation of polyurea bonds through the reaction of the water and isocyanate.
Surfactants can be used as wetting agents and to assist in mixing and dispersing the inorganic particulate material in a composite. Surfactants can also stabilize and control the size of bubbles formed during the foaming event and the resultant cell structure. Surfactants can be used, for example, in amounts below about 0.5 wt % based on the total weight of the mixture. Examples of surfactants useful with the polyurethanes described herein include anionic, non-ionic and cationic surfactants. For example, silicone surfactants such as DC-197 and DC-193 (Air Products; Allentown, PA) can be used.
The addition of excess foaming or blowing agents above what is needed to complete the foaming reaction can add strength and stiffness to the composite material, improve the water resistance of the composite material, and increase the thickness and durability of the outer skin of the composite material. Such excessive blowing agent may produce a vigorously foaming reaction product. To contain the reaction product, a forming device that contains the pressure or restrains the materials from expanding beyond the design limits may be used, such as a stationary or continuous mold.
Low molecular weight reactants such as chain-extenders and/or crosslinkers can be included in the composite materials described herein. These reactants help the polyurethane system to distribute and contain the inorganic filler and/or fibers within the composite material. Chain-extenders are difunctional molecules, such as diamines, that can polymerize to lengthen the urethane polymer chains.
Examples of diamine chain-extenders include ethylene diamine, 4,4'-methylenebis(2-chloroaniline) (MBOCA), diethyltoluene diamine (DETDA); and aromatic diamines such as Unilink 4200 (commercially available from UOP). Crosslinkers are tri-or greater functional molecules that can integrate into a polymer chain through two functionalities and provide one or more further functionalities (i.e., linkage sites) to crosslink to additional polymer chains. Examples of amine-based crosslinkers include diethanolamine and triethanolamine.
Coupling agents and other surface treatments such as viscosity reducers, flow control agents, or dispersing agents can be added directly to the filler or fiber, or incorporated prior to, during, and/or after the mixing and reaction of the composite material. Coupling agents can allow higher filler loadings of an inorganic filler such as fly ash and may be used in small quantities. For example, the composite material may comprise about 0.01 wt % to about 0.5 wt % of a coupling agent. Examples of coupling agents useful with the composite materials described herein include Ken-React LICA 38 and KEN-React KR 55 (Kenrich Petrochemicals; Bayonne, NJ).
Examples of dispersing agents useful with the composite materials described herein include JEFFSPERSE X3202, JEFFSPERSE X3202RF, and JEFFSPERSE X3204 (Huntsman Polyurethanes; Geismar, LA).
Ultraviolet light stabilizers, such as UV absorbers, can be added to the composite materials described herein. Examples of UV light stabilizers include hindered amine type stabilizers and opaque pigments like carbon black powder.
Fire retardants can be included to increase the flame or fire resistance of the composite material. Antimicrobials can be used to limit the growth of mildew and other organisms on the surface of the composite. Antioxidants, such as phenolic antioxidants, can also be added. Antioxidants provide increased UV protection, as well as thermal oxidation protection.
Pigments or dyes can optionally be added to the composite materials described herein. An example of a pigment is iron oxide, which can be added in amounts ranging from about 2 wt % to about 7 wt %, based on the total weight of the composite material.
Examples of compositions illustrating aspects of the composites as described herein are shown in Tables 1-3. Exemplary ingredients for a first fly ash filled composite material (Composite 1) are shown in Table 1. In Composite 1, fly ash filler and glycerin both have recyclable content, and castor oil has renewable content. The surfactants, catalysts, water, and glass fibers are not generally considered to have renewable or recyclable content. The use of castor oil as the polyol provides a polyurethane component of the composite (based only on the polyols and isocyanates) with a total environmental content of 41.66 wt %, and the total environmental content for Composite 1 is 79.84%.
Table 1: Composite 1 Ingredient Units Renewable Renewable Recyclable Content, % Content Units Units Fl ash 711.38 0 - 711.38 Castor Oil 85.00 100 85.00 -Glycerin 15.00 0 - 15.00 Surfactant 1.00 0 - -Catalyst 1.00 0 - -Water 1.80 0 - -Fiber 60.97 0 - -Isocyanate 140.04 0 - -Delayed catalyst 0.06 0 - -Total Units 1016.25 Total Renewable Units - - 85.00 -Total Recyclable Units - - - 726.38 % Fly Ash 70.00 % Renewable Content 8.36 % Recyclable Content 71.48 Total Environmental 79.84 Content Exemplary ingredients for a second fly ash filled composite material (Composite 2) are shown in Table 2. Composite 2 includes Ecopol 131, which is understood from the product literature to include 40% soybean oil (renewable content) and 40% recycled polyester (recyclable content). In Composite 2, the fly ash filler contains recyclable content, and castor oil has renewable content. In this example, surfactants, catalysts, water, and glass fibers are not considered to contain renewable or recyclable content. The use of castor oil as the polyol provides a polyurethane component of the composite with a total environmental content of 38.97 wt %, and the total environmental content for Composite 2 is 79.19%.
Table 2: Composite 2 Ingredient Units Renewable Renewable Recyclable Content, % Content Units Units Fly ash 639.54 0 - 639.54 Castor Oil 20.00 100 20.00 -Ecopol 131 80.00 40 32.00 32.00 Surfactant 1.00 0 - -Catalyst 1.00 0 - -Water 1.70 0 - -Fiber 54.82 0 - -Isocyanate 115.55 0 - -Delayed catalyst 0.02 0 - -Total Units 913.63 Total Renewable - - 52.00 -Content Units Total Recyclable Units - - - 671.54 % Fly Ash 70.00 % Renewable-Content 5.69 % Recyclable Content 73.50 Total Environmental 79.19 Content Exemplary ingredients for a third fly ash filled composite material (Composite 3) are shown in Table 3. In Composite 3, fly ash filler and glycerin contain recyclable content, and castor oil contains renewable content. The surfactants, catalysts, water, and glass fibers are not considered to contain renewable or recyclable content. The use of castor oil as the polyol provides a polyurethane component of the composite with a total environmental content of 37.45 wt %, and the total environmental content for Composite 3 is 78.83%.
Examples of blowing agents include organic blowing agents, such as halogenated hydrocarbons, acetone, hexanes, and other materials that have a boiling point below the reaction temperature. Chemical foaming agents include azodicarbonamides (e.g., Celogen manufactured by Lion Copolymer Geismar); and other materials that react at the reaction temperature to form gases such as carbon dioxide. Water is an exemplary foaming agent that reacts with isocyanate to yield carbon dioxide. The presence of water as an added component or in the filler also can result in the formation of polyurea bonds through the reaction of the water and isocyanate.
Surfactants can be used as wetting agents and to assist in mixing and dispersing the inorganic particulate material in a composite. Surfactants can also stabilize and control the size of bubbles formed during the foaming event and the resultant cell structure. Surfactants can be used, for example, in amounts below about 0.5 wt % based on the total weight of the mixture. Examples of surfactants useful with the polyurethanes described herein include anionic, non-ionic and cationic surfactants. For example, silicone surfactants such as DC-197 and DC-193 (Air Products; Allentown, PA) can be used.
The addition of excess foaming or blowing agents above what is needed to complete the foaming reaction can add strength and stiffness to the composite material, improve the water resistance of the composite material, and increase the thickness and durability of the outer skin of the composite material. Such excessive blowing agent may produce a vigorously foaming reaction product. To contain the reaction product, a forming device that contains the pressure or restrains the materials from expanding beyond the design limits may be used, such as a stationary or continuous mold.
Low molecular weight reactants such as chain-extenders and/or crosslinkers can be included in the composite materials described herein. These reactants help the polyurethane system to distribute and contain the inorganic filler and/or fibers within the composite material. Chain-extenders are difunctional molecules, such as diamines, that can polymerize to lengthen the urethane polymer chains.
Examples of diamine chain-extenders include ethylene diamine, 4,4'-methylenebis(2-chloroaniline) (MBOCA), diethyltoluene diamine (DETDA); and aromatic diamines such as Unilink 4200 (commercially available from UOP). Crosslinkers are tri-or greater functional molecules that can integrate into a polymer chain through two functionalities and provide one or more further functionalities (i.e., linkage sites) to crosslink to additional polymer chains. Examples of amine-based crosslinkers include diethanolamine and triethanolamine.
Coupling agents and other surface treatments such as viscosity reducers, flow control agents, or dispersing agents can be added directly to the filler or fiber, or incorporated prior to, during, and/or after the mixing and reaction of the composite material. Coupling agents can allow higher filler loadings of an inorganic filler such as fly ash and may be used in small quantities. For example, the composite material may comprise about 0.01 wt % to about 0.5 wt % of a coupling agent. Examples of coupling agents useful with the composite materials described herein include Ken-React LICA 38 and KEN-React KR 55 (Kenrich Petrochemicals; Bayonne, NJ).
Examples of dispersing agents useful with the composite materials described herein include JEFFSPERSE X3202, JEFFSPERSE X3202RF, and JEFFSPERSE X3204 (Huntsman Polyurethanes; Geismar, LA).
Ultraviolet light stabilizers, such as UV absorbers, can be added to the composite materials described herein. Examples of UV light stabilizers include hindered amine type stabilizers and opaque pigments like carbon black powder.
Fire retardants can be included to increase the flame or fire resistance of the composite material. Antimicrobials can be used to limit the growth of mildew and other organisms on the surface of the composite. Antioxidants, such as phenolic antioxidants, can also be added. Antioxidants provide increased UV protection, as well as thermal oxidation protection.
Pigments or dyes can optionally be added to the composite materials described herein. An example of a pigment is iron oxide, which can be added in amounts ranging from about 2 wt % to about 7 wt %, based on the total weight of the composite material.
Examples of compositions illustrating aspects of the composites as described herein are shown in Tables 1-3. Exemplary ingredients for a first fly ash filled composite material (Composite 1) are shown in Table 1. In Composite 1, fly ash filler and glycerin both have recyclable content, and castor oil has renewable content. The surfactants, catalysts, water, and glass fibers are not generally considered to have renewable or recyclable content. The use of castor oil as the polyol provides a polyurethane component of the composite (based only on the polyols and isocyanates) with a total environmental content of 41.66 wt %, and the total environmental content for Composite 1 is 79.84%.
Table 1: Composite 1 Ingredient Units Renewable Renewable Recyclable Content, % Content Units Units Fl ash 711.38 0 - 711.38 Castor Oil 85.00 100 85.00 -Glycerin 15.00 0 - 15.00 Surfactant 1.00 0 - -Catalyst 1.00 0 - -Water 1.80 0 - -Fiber 60.97 0 - -Isocyanate 140.04 0 - -Delayed catalyst 0.06 0 - -Total Units 1016.25 Total Renewable Units - - 85.00 -Total Recyclable Units - - - 726.38 % Fly Ash 70.00 % Renewable Content 8.36 % Recyclable Content 71.48 Total Environmental 79.84 Content Exemplary ingredients for a second fly ash filled composite material (Composite 2) are shown in Table 2. Composite 2 includes Ecopol 131, which is understood from the product literature to include 40% soybean oil (renewable content) and 40% recycled polyester (recyclable content). In Composite 2, the fly ash filler contains recyclable content, and castor oil has renewable content. In this example, surfactants, catalysts, water, and glass fibers are not considered to contain renewable or recyclable content. The use of castor oil as the polyol provides a polyurethane component of the composite with a total environmental content of 38.97 wt %, and the total environmental content for Composite 2 is 79.19%.
Table 2: Composite 2 Ingredient Units Renewable Renewable Recyclable Content, % Content Units Units Fly ash 639.54 0 - 639.54 Castor Oil 20.00 100 20.00 -Ecopol 131 80.00 40 32.00 32.00 Surfactant 1.00 0 - -Catalyst 1.00 0 - -Water 1.70 0 - -Fiber 54.82 0 - -Isocyanate 115.55 0 - -Delayed catalyst 0.02 0 - -Total Units 913.63 Total Renewable - - 52.00 -Content Units Total Recyclable Units - - - 671.54 % Fly Ash 70.00 % Renewable-Content 5.69 % Recyclable Content 73.50 Total Environmental 79.19 Content Exemplary ingredients for a third fly ash filled composite material (Composite 3) are shown in Table 3. In Composite 3, fly ash filler and glycerin contain recyclable content, and castor oil contains renewable content. The surfactants, catalysts, water, and glass fibers are not considered to contain renewable or recyclable content. The use of castor oil as the polyol provides a polyurethane component of the composite with a total environmental content of 37.45 wt %, and the total environmental content for Composite 3 is 78.83%.
Table 3: Composite 3 Ingredient Units Renewable Renewable Recyclable Content, % Units Units Fly ash 665.03 0 - 665.03 Castor Oil 18.00 100 18.00 -Ecopol 131 80.00 40 32.00 32.00 Glycerin 2.00 0 - 2.00 Surfactant 1.00 0 - -Catalyst 1.00 0 - -Water 1.70 0 - -Fiber 57.00 0 - -Isocyanate 124.29 0 - -Delayed catalyst 0.02 0 - -Total Units 950.04 Total Renewable Units - - 50.00 -Total Recyclable Units - - - 699.03 % Fly Ash 70.00 % Renewable Content 5.26 % Recyclable Content 73.57 Total Environmental 78.83 Content Composites 1-3 used as examples above are all based upon a filler loading of about 70 wt % fly ash. However, filler loading can be increased to about 85 wt % fly ash or greater, which would increase the total environmental content (other component amounts being held constant).
A method of preparing a composite material is also described herein. The method includes mixing (1) an isocyanate selected from the group consisting of diisocyanates, polyisocyanates, and mixtures thereof, (2) at least two polyols, the at least two polyols including (i) a high hydroxyl number polyol selected from polyether polyols and polyester polyols, the high hydroxyl number polyol having a hydroxyl number greater than 250 and being from about 1% to about 25% by weight of the total polyol content used to form the polyurethane, and (ii) a low hydroxyl number polyol selected from polyether polyols and polyester polyols, the low hydroxyl number polyol having a hydroxyl number of 250 or lower; (3) coal ash (e.g., fly ash) present in amounts from about 40% to about 90% by weight of the composite material;
and (4) a catalyst. The isocyanate and the at least two polyols are allowed to react in the presence of the coal ash and catalyst to form the composite material.
The composite material can be produced using a batch, semi-batch, or continuous process. At least a portion of the mixing step, reacting step, or both, can be conducted in a mixing apparatus such as a high speed mixer or an extruder.
The method can further include the step of extruding the resulting composite material through a die or nozzle. In some embodiments, a mixing step of the method used to prepare the composite materials described herein includes: (1) mixing the polyol and fly ash; (2) mixing the isocyanate with the polyol and the fly ash; and (3) mixing the catalyst with the isocyanate, the polyol, and the fly ash. In some embodiments, a mixing step of the method used to prepare the composite materials described herein includes mixing the liquid ingredients (i.e., the polyol, isocyanate, catalyst, surfactants, and water) and then combining the mixed liquid ingredients with the fly ash and optional fiber. As the composite material exits the die or nozzle, the composite material may be placed in a mold for post-extrusion curing and shaping.
For example, the composite material can be allowed to cure in individual molds or it can be allowed to cure in a continuous forming system such as a belt molding system.
An ultrasonic device can be used for enhanced mixing and/or wetting of the various components of the composite materials described herein. Such enhanced mixing and/or wetting can allow a high concentration of filler (e.g., fly ash) to be mixed with the polyurethane matrix, including about 40 wt %, about 50 wt %, about 60 wt %, about 70 wt %, about 80 wt %, and about 90 wt % of the inorganic filler.
The ultrasonic device produces an ultrasound of a certain frequency that can be varied during the mixing and/or extrusion process. The ultrasonic device useful in the preparation of composite materials described herein can be attached to or adjacent to an extruder and/or mixer. For example, the ultrasonic device can be attached to a die or nozzle or to the port of an extruder or mixer. An ultrasonic device may provide de-aeration of undesired gas bubbles and better mixing for the other components, such as blowing agents, surfactants, and catalysts.
The composite materials described herein can be foamed. The at least two polyols and the isocyanate can be allowed to produce a foamed composite material after mixing the components according to the methods described herein. The composite materials described herein can be formed while they are actively foaming or after they have foamed. For example, the material can be placed under the pressure of a mold cavity prior to or during the foaming of the composite material.
When a foaming composite material is molded by a belt molding system into a product shape, the pressure that the foamed part exerts on the belts impacts the resulting mechanical properties. For example, as the pressure of the foaming increases and if the belt system can hold this pressure without the belts separating, then the product may have higher flexural strength than if the belts allowed leaking or pressure drop.
The composite materials described herein can be formed into shaped articles and used in various applications including building materials. Examples of such building materials include siding material, roof coatings, roof tiles, roofing material, carpet backing, flexible or rigid foams such as automotive foams (e.g., for dashboard, seats, or roofing), component coating, and other shaped articles. Examples of shaped articles made using composite materials described herein include roofing material such as roof tile shingles; siding material; trim boards; carpet backing;
synthetic lumber; building panels; scaffolding; cast molded products; decking materials;
fencing materials; marine lumber; doors; door parts; moldings; sills; stone;
masonry;
brick products; posts; signs; guard rails; retaining walls; park benches;
tables; slats;
and railroad ties. The composite materials described herein further can be used as reinforcement of composite structural members including building materials such as doors; windows; furniture; and cabinets and for well and concrete repair. The composite materials described herein also can be used to fill gaps, particularly to increase the strength of solid surface articles and/or structural components.
The composite materials can be flexible, semi-rigid, or rigid foams. In some embodiments, the flexible foam is reversibly deformable (i.e., resilient) and can include open cells. A 8" x 1" x 1" piece of a flexible foam can generally wrap around a 1" diameter mandrel at room temperature without rupture or fracture.
Flexible foams also generally have a density of less than 5 lb/ft3 (e.g. 1 to 5 lb/ft).
In some embodiments, the rigid foam is irreversibly deformable and can be highly crosslinked and/or can include closed cells. Rigid foams generally have a density of 5 lb/ft3 or greater (e.g. 5 to 60 lb/ft3, 20 to 55 lb/ft3, or 30 to 50 lb/ft).
A method of preparing a composite material is also described herein. The method includes mixing (1) an isocyanate selected from the group consisting of diisocyanates, polyisocyanates, and mixtures thereof, (2) at least two polyols, the at least two polyols including (i) a high hydroxyl number polyol selected from polyether polyols and polyester polyols, the high hydroxyl number polyol having a hydroxyl number greater than 250 and being from about 1% to about 25% by weight of the total polyol content used to form the polyurethane, and (ii) a low hydroxyl number polyol selected from polyether polyols and polyester polyols, the low hydroxyl number polyol having a hydroxyl number of 250 or lower; (3) coal ash (e.g., fly ash) present in amounts from about 40% to about 90% by weight of the composite material;
and (4) a catalyst. The isocyanate and the at least two polyols are allowed to react in the presence of the coal ash and catalyst to form the composite material.
The composite material can be produced using a batch, semi-batch, or continuous process. At least a portion of the mixing step, reacting step, or both, can be conducted in a mixing apparatus such as a high speed mixer or an extruder.
The method can further include the step of extruding the resulting composite material through a die or nozzle. In some embodiments, a mixing step of the method used to prepare the composite materials described herein includes: (1) mixing the polyol and fly ash; (2) mixing the isocyanate with the polyol and the fly ash; and (3) mixing the catalyst with the isocyanate, the polyol, and the fly ash. In some embodiments, a mixing step of the method used to prepare the composite materials described herein includes mixing the liquid ingredients (i.e., the polyol, isocyanate, catalyst, surfactants, and water) and then combining the mixed liquid ingredients with the fly ash and optional fiber. As the composite material exits the die or nozzle, the composite material may be placed in a mold for post-extrusion curing and shaping.
For example, the composite material can be allowed to cure in individual molds or it can be allowed to cure in a continuous forming system such as a belt molding system.
An ultrasonic device can be used for enhanced mixing and/or wetting of the various components of the composite materials described herein. Such enhanced mixing and/or wetting can allow a high concentration of filler (e.g., fly ash) to be mixed with the polyurethane matrix, including about 40 wt %, about 50 wt %, about 60 wt %, about 70 wt %, about 80 wt %, and about 90 wt % of the inorganic filler.
The ultrasonic device produces an ultrasound of a certain frequency that can be varied during the mixing and/or extrusion process. The ultrasonic device useful in the preparation of composite materials described herein can be attached to or adjacent to an extruder and/or mixer. For example, the ultrasonic device can be attached to a die or nozzle or to the port of an extruder or mixer. An ultrasonic device may provide de-aeration of undesired gas bubbles and better mixing for the other components, such as blowing agents, surfactants, and catalysts.
The composite materials described herein can be foamed. The at least two polyols and the isocyanate can be allowed to produce a foamed composite material after mixing the components according to the methods described herein. The composite materials described herein can be formed while they are actively foaming or after they have foamed. For example, the material can be placed under the pressure of a mold cavity prior to or during the foaming of the composite material.
When a foaming composite material is molded by a belt molding system into a product shape, the pressure that the foamed part exerts on the belts impacts the resulting mechanical properties. For example, as the pressure of the foaming increases and if the belt system can hold this pressure without the belts separating, then the product may have higher flexural strength than if the belts allowed leaking or pressure drop.
The composite materials described herein can be formed into shaped articles and used in various applications including building materials. Examples of such building materials include siding material, roof coatings, roof tiles, roofing material, carpet backing, flexible or rigid foams such as automotive foams (e.g., for dashboard, seats, or roofing), component coating, and other shaped articles. Examples of shaped articles made using composite materials described herein include roofing material such as roof tile shingles; siding material; trim boards; carpet backing;
synthetic lumber; building panels; scaffolding; cast molded products; decking materials;
fencing materials; marine lumber; doors; door parts; moldings; sills; stone;
masonry;
brick products; posts; signs; guard rails; retaining walls; park benches;
tables; slats;
and railroad ties. The composite materials described herein further can be used as reinforcement of composite structural members including building materials such as doors; windows; furniture; and cabinets and for well and concrete repair. The composite materials described herein also can be used to fill gaps, particularly to increase the strength of solid surface articles and/or structural components.
The composite materials can be flexible, semi-rigid, or rigid foams. In some embodiments, the flexible foam is reversibly deformable (i.e., resilient) and can include open cells. A 8" x 1" x 1" piece of a flexible foam can generally wrap around a 1" diameter mandrel at room temperature without rupture or fracture.
Flexible foams also generally have a density of less than 5 lb/ft3 (e.g. 1 to 5 lb/ft).
In some embodiments, the rigid foam is irreversibly deformable and can be highly crosslinked and/or can include closed cells. Rigid foams generally have a density of 5 lb/ft3 or greater (e.g. 5 to 60 lb/ft3, 20 to 55 lb/ft3, or 30 to 50 lb/ft).
The composites and methods of the appended claims are not limited in scope by the specific composites and methods described herein, which are intended as illustrations of a few aspects of the claims and any composites and methods that are functionally equivalent are intended to fall within the scope of the claims.
Various modifications of the composites and methods in addition to those shown and described herein are intended to fall within the scope of the appended claims.
Further, while only certain representative composite materials and method steps disclosed herein are specifically described, other combinations of the composite materials and method steps also are intended to fall within the scope of the appended claims, even if not specifically recited. Thus, a combination of steps, elements, components, or constituents may be explicitly mentioned herein; however, other combinations of steps, elements, components, and constituents are included, even though not explicitly stated. The term comprising and variations thereof as used herein is used synonymously with the term including and variations thereof and are open, non-limiting terms. Although the terms comprising and including have been used herein to describe various embodiments, the terms "consisting essentially of' and "consisting of' can be used in place of "comprising" and "including" to provide for more specific embodiments of the invention and are also disclosed.
Various modifications of the composites and methods in addition to those shown and described herein are intended to fall within the scope of the appended claims.
Further, while only certain representative composite materials and method steps disclosed herein are specifically described, other combinations of the composite materials and method steps also are intended to fall within the scope of the appended claims, even if not specifically recited. Thus, a combination of steps, elements, components, or constituents may be explicitly mentioned herein; however, other combinations of steps, elements, components, and constituents are included, even though not explicitly stated. The term comprising and variations thereof as used herein is used synonymously with the term including and variations thereof and are open, non-limiting terms. Although the terms comprising and including have been used herein to describe various embodiments, the terms "consisting essentially of' and "consisting of' can be used in place of "comprising" and "including" to provide for more specific embodiments of the invention and are also disclosed.
Claims (43)
1. A composite material comprising:
a polyurethane formed by the reaction of an isocyanate selected from the group consisting of diisocyanates, polyisocyanates and mixtures thereof, and at least two polyols, the at least two polyols comprising:
a high hydroxyl number polyol selected from the group consisting of polyether polyols and polyester polyols, the high hydroxyl number polyol having a hydroxyl number greater than 250 and having 75% or greater primary hydroxyl groups comprising from about 1% to about 25% by weight of the total polyol content used to form the polyurethane, and a low hydroxyl number polyol selected from the group consisting of polyether polyols and polyester polyols, the low hydroxyl number polyol having a hydroxyl number of 250 or lower; and from about 40% to about 90% by weight coal ash.
a polyurethane formed by the reaction of an isocyanate selected from the group consisting of diisocyanates, polyisocyanates and mixtures thereof, and at least two polyols, the at least two polyols comprising:
a high hydroxyl number polyol selected from the group consisting of polyether polyols and polyester polyols, the high hydroxyl number polyol having a hydroxyl number greater than 250 and having 75% or greater primary hydroxyl groups comprising from about 1% to about 25% by weight of the total polyol content used to form the polyurethane, and a low hydroxyl number polyol selected from the group consisting of polyether polyols and polyester polyols, the low hydroxyl number polyol having a hydroxyl number of 250 or lower; and from about 40% to about 90% by weight coal ash.
2. A composite material comprising:
a polyurethane formed by the reaction of an isocyanate selected from the group consisting of diisocyanates, polyisocyanates and mixtures thereof, and at least two polyols, the at least two polyols comprising:
a high hydroxyl number polyol selected from the group consisting of polyether polyols and polyester polyols, the high hydroxyl number polyol having a hydroxyl number greater than 250 and comprising from about 1% to about 25% by weight of the total polyol content used to form the polyurethane, and a low hydroxyl number polyol selected from the group consisting of polyether polyols and polyester polyols, the low hydroxyl number polyol having a hydroxyl number of lower than 180; and from about 40% to about 90% by weight coal ash.
a polyurethane formed by the reaction of an isocyanate selected from the group consisting of diisocyanates, polyisocyanates and mixtures thereof, and at least two polyols, the at least two polyols comprising:
a high hydroxyl number polyol selected from the group consisting of polyether polyols and polyester polyols, the high hydroxyl number polyol having a hydroxyl number greater than 250 and comprising from about 1% to about 25% by weight of the total polyol content used to form the polyurethane, and a low hydroxyl number polyol selected from the group consisting of polyether polyols and polyester polyols, the low hydroxyl number polyol having a hydroxyl number of lower than 180; and from about 40% to about 90% by weight coal ash.
3. The composite material of claim 2, wherein the low hydroxyl number polyol has a hydroxyl number of lower than 170.
4. The composite material of claim 2 or 3, wherein the high hydroxyl number polyol includes a polyol having 75% or greater primary hydroxyl groups.
5. The composite material of any of claims 1-4, wherein the coal ash is fly ash.
6. The composite material of any of claims 1-5, wherein one or more of the high hydroxyl number polyol and the low hydroxyl number polyol is a plant-based polyol.
7. The composite material of any of claims 1-6, wherein the high hydroxyl number polyol includes glycerin.
8. The composite material of any of claims 1-7, wherein the low hydroxyl number polyol includes castor oil and the high hydroxyl number polyol includes glycerin.
9. The composite material of any of claims 1-8, wherein the low hydroxyl number polyol includes castor oil and the high hydroxyl number polyol includes a soybean oil-based polyol.
10. The composite material of claim 9, wherein the soybean oil-based polyol is formed by the reaction of a soybean oil and a polyester.
11. The composite material of claim 10, wherein the soybean oil and polyester based polyol is prepared using recycled polyester.
12. The composite material of any of claims 1-11, wherein the high hydroxyl number polyol is present in an amount from about 1% to about 15%.
13. The composite material of any of claims 1-12, wherein the polyurethane component has a total environmental content of greater than 35%.
14. The composite material of any of claims 1-13, wherein the polyurethane component has a total environmental content of greater than 40%.
15. The composite material of any of claims 1-14, wherein the polyurethane component has a total environmental content of greater than 45%.
16. The composite material of any of claims 1-15, wherein the polyurethane component has a total environmental content of about 50%.
17. The composite material of any of claims 1-16, wherein the composite material has a total environmental content of greater than 75%.
18. The composite material of any of claims 1-17, wherein the composite material has a total environmental content of greater than 80%.
19. The composite material of any of claims 1-18, wherein the composite material has a total environmental content of greater than about 85%.
20. The composite material of any of claims 1-19, wherein the composite material is foamed.
21. The composite material of any of claims 1-20, further comprising glass fibers.
22. The composite material of any of claims 1-21, wherein the fly ash is from about 60% to about 85% by weight.
23. A building material comprising the composite material of any of claims 1-22.
24. The building material of claim 23, wherein the building material is selected from the group consisting of siding material, carpet backing, building panels, and roofing material.
25. A method of preparing a composite material comprising:
mixing (1) an isocyanate selected from the group consisting of diisocyanates, polyisocyanates and mixtures thereof, (2) at least two polyols, the at least two polyols comprising (i) a high hydroxyl number polyol selected from the group consisting of polyether polyols and polyester polyols, the high hydroxyl number polyol having a hydroxyl number greater than 250 and having 75% or greater primary hydroxyl groups and comprising from about 1% to about 25% by weight of the total polyol content used to form the polyurethane, and (ii) a low hydroxyl number polyol selected from the group consisting of polyether polyols and polyester polyols, the low hydroxyl number polyol having a hydroxyl number of 250 or lower, (3) coal ash, and (4) a catalyst; and allowing the isocyanate and the at least two polyols to react in the presence of the coal ash and catalyst to form the composite material, wherein the amount of coal ash added in the mixing step comprises from about 40% to about 90% by weight of the composite material.
mixing (1) an isocyanate selected from the group consisting of diisocyanates, polyisocyanates and mixtures thereof, (2) at least two polyols, the at least two polyols comprising (i) a high hydroxyl number polyol selected from the group consisting of polyether polyols and polyester polyols, the high hydroxyl number polyol having a hydroxyl number greater than 250 and having 75% or greater primary hydroxyl groups and comprising from about 1% to about 25% by weight of the total polyol content used to form the polyurethane, and (ii) a low hydroxyl number polyol selected from the group consisting of polyether polyols and polyester polyols, the low hydroxyl number polyol having a hydroxyl number of 250 or lower, (3) coal ash, and (4) a catalyst; and allowing the isocyanate and the at least two polyols to react in the presence of the coal ash and catalyst to form the composite material, wherein the amount of coal ash added in the mixing step comprises from about 40% to about 90% by weight of the composite material.
26. A method of preparing a composite material comprising:
mixing (1) an isocyanate selected from the group consisting of diisocyanates, polyisocyanates and mixtures thereof, (2) at least two polyols, the at least two polyols comprising (i) a high hydroxyl number polyol selected from the group consisting of polyether polyols and polyester polyols, the high hydroxyl number polyol having a hydroxyl number greater than 250 and comprising from about 1% to about 25% by weight of the total polyol content used to form the polyurethane, and (ii) a low hydroxyl number polyol selected from the group consisting of polyether polyols and polyester polyols, the low hydroxyl number polyol having a hydroxyl number of lower than 180, (3) coal ash, and (4) a catalyst; and allowing the isocyanate and the at least two polyols to react in the presence of the coal ash and catalyst to form the composite material, wherein the amount of coal ash added in the mixing step comprises from about 40% to about 90% by weight of the composite material.
mixing (1) an isocyanate selected from the group consisting of diisocyanates, polyisocyanates and mixtures thereof, (2) at least two polyols, the at least two polyols comprising (i) a high hydroxyl number polyol selected from the group consisting of polyether polyols and polyester polyols, the high hydroxyl number polyol having a hydroxyl number greater than 250 and comprising from about 1% to about 25% by weight of the total polyol content used to form the polyurethane, and (ii) a low hydroxyl number polyol selected from the group consisting of polyether polyols and polyester polyols, the low hydroxyl number polyol having a hydroxyl number of lower than 180, (3) coal ash, and (4) a catalyst; and allowing the isocyanate and the at least two polyols to react in the presence of the coal ash and catalyst to form the composite material, wherein the amount of coal ash added in the mixing step comprises from about 40% to about 90% by weight of the composite material.
27. The method of claim 26, wherein the low hydroxyl number polyol has a hydroxyl number of lower than 170.
28. The method of claim 26 or 27, wherein the high hydroxyl number polyol includes a polyol having 75% or greater primary hydroxyl groups.
29. The method of any of claims 25-28, wherein the coal ash is fly ash.
30. The method of any of claims 25-29, wherein the high hydroxyl number polyol includes glycerin.
31. The method of any of claims 25-30, wherein the low hydroxyl number polyol includes castor oil and the high hydroxyl number polyol includes glycerin.
32. The method of any of claims 25-31, wherein the low hydroxyl number polyol includes castor oil and the high hydroxyl number polyol includes a soybean oil-based polyol.
33. The method of claim 32, wherein the soybean oil-based polyol is formed by the reaction of a soybean oil and a polyester.
34. The method of claim 33, wherein the soybean oil and polyester based polyol is prepared using recycled polyester.
35. The method of any of claims 25-34, wherein the high hydroxyl number polyol is present in an amount from 1% to about 15%.
36. The method of any of claims 25-35, wherein the total environmental content of a combination of the isocyanate and polyol components is greater than 35%.
37. The method of any of claims 25-36, wherein the total environmental content of a combination of the isocyanate and polyol components is greater than 40%.
38. The method of any of claims 25-37, wherein the total environmental content of a combination of the isocyanate and polyol components is greater than 45%.
39. The method of any of claims 25-38, wherein the total environmental content of a combination of the isocyanate and polyol components is about 50%.
40. The method of any of claims 25-39, wherein the composite material has a total environmental content of greater than 75%.
41. The method of any of claims 25-40, wherein the composite material has a total environmental content of greater than 80%.
42. The method of any of claims 25-41, wherein the composite material has a total environmental content of greater than about 85%.
43. The method of any of claims 25-42, wherein the mixing step further comprises mixing glass fibers.
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CA2748220A1 (en) | 2008-12-19 | 2010-07-15 | Dennert Poraver Gmbh | Open-pore formed body and method for the production thereof |
DE102008063815A1 (en) | 2008-12-19 | 2010-06-24 | Hans-Peter Kohlstadt | Open porous molded body based on inorganic light-granules with hydrophobic surface, and organic binders, useful e.g. as furniture panels, preferably for countertops, and as plates for electrical appliances such as refrigerators |
DE202008016807U1 (en) | 2008-12-19 | 2010-05-20 | Kohlstadt, Hans-Peter | Open-pore shaped body |
WO2011005706A2 (en) | 2009-07-06 | 2011-01-13 | Boral Material Technologies Inc. | Fiber feed system for extruder for use in filled polymeric products |
JP5237913B2 (en) | 2009-09-27 | 2013-07-17 | 株式会社微酸性電解水研究所 | Preparation method of molecular hypochlorous acid solution by ion exchange and molecular hypochlorous acid solution |
JP5237914B2 (en) | 2009-09-30 | 2013-07-17 | グンゼ株式会社 | Measuring device, biosensor, and measurement display device for substrate component amount of specimen |
-
2010
- 2010-08-12 US US12/855,380 patent/US8846776B2/en active Active
- 2010-08-13 AU AU2010282402A patent/AU2010282402A1/en not_active Abandoned
- 2010-08-13 CA CA2770914A patent/CA2770914A1/en not_active Abandoned
- 2010-08-13 WO PCT/US2010/045454 patent/WO2011020004A1/en active Application Filing
Also Published As
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WO2011020004A1 (en) | 2011-02-17 |
US20110086934A1 (en) | 2011-04-14 |
US8846776B2 (en) | 2014-09-30 |
AU2010282402A1 (en) | 2012-03-01 |
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